Theoretical study of the interaction mechanism of single-electron halogen bond complexes H_3C…Br-Y(Y=H,CN,NC,CCH,C_2H_3)

作     者：LI ZhiFeng1,SHI XiaoNing1,TANG HuiAn1 & ZHANG JunYan2 1College of Life Science and Chemistry,Tianshui Normal University,Tianshui 741001,China 2Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China 

作者机构：College of Life Science and Chemistry Tianshui Normal University Tianshui China Lanzhou Institute of Chemical Physics Chinese Academy of Sciences Lanzhou China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2010年第53卷第1期

页      面：216-225页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the Foundation of the Education Committee of Gansu Province (Grant No. 0708-11) "Qinglan" Talent Engineering Funds of Tianshui Normal University 

主　　题：single-electron halogen bond single-electron hydrogen bond single-electron lithium bond MP2 DFT NBO AIM 

摘      要：The characteristics and structures of single-electron halogen bond complexes H3C…Br-Y(Y = H,CCH,CN,NC,C2H3) have been investigated by theoretical calculation *** geometries were optimized and frequencies calculated at the B3LYP/6-311++G *** interaction energies were corrected for basis set superposition error(BSSE) and the wavefunctions obtained by the natural bond orbital(NBO) and atom in molecule(AIM) analyses at the MP2/6-311++G *** each H3C…Br-Y complex,a single-electron Br bond is formed between the unpaired electron of the CH3(electron donor) radical and the Br atom of Br-Y(electron acceptor);this kind of single-electron bromine bond also possesses the character of athree-electron bond.Due to the formation of the single-electron Br bond,the C-H bonds of the CH3 radical bend away from the Br-Y moiety and the Br-Y bond elongates,giving red-shifted single-electron Br bond *** effects of substituents,hybridization of the carbon atom,and solvent on the properties of the complexes have been *** strengths of single-electron hydrogen bonds,single-electron halogen bonds and single-electron lithium bonds have been *** addition,the single-electron halogen bond system is discussed in the light of the first three criteria for hydrogen bonding proposed by Popelier.